Ester-linked acylated aminoalcohols and method of making same



Patented Aug. 7, 1945 ESTER-LINKED ACYLATED AMINOALCO- HOLS AND METHOD OF MAKING SAME Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a

corporation of Delaware No Drawing. Original application June 15, 1942,

Serial No. 447,161. Divided and this application August 2, 1943, Serial No. 497,128

12 Claims. This invention relates to a new chemical product or composition of matter, our present application being a division of our pending application dated July 18, 1944.

resolution of crude oil emulsions.

chemical product or compound.

after indicated.

of crude oil.

eral procedures.

and momentarily R1 (OH) m.

ester with the selected oxyalkylated glycerol.

Glycerol may be conveniently indicated by the following formula:

GB Serial No. 447,161, filed June 15, 1942, which sub- CMZOH sequently matured as U. S, Patent No. 2,353,704, 5

The main object of our invention is to provide If treated with a oxyalkylatmg agent, and mot gf ff gf 2%? g;- mentarlly consideration will be limited to an y p e or use 5 e 5 er n e 10 oxyethylating agent, one may obtain an oxy- Another object of our invention is to provide ethylated glycerol of the following formula: 9. practicable method for manufacturing said new (CIHiOM v c n 0 c H om: Although one of the primary objects of our a B 8( H invention is to provide a new compound or composition of matter, that is an efiicient demulsiin which the value of may vary fr m 3 t 10 timesziinzzsisazzizfistirs;is values 0W g gf If d 'n ca e or-. ter is adapted for use in other arts, as hereing gigf carboxy am e 1 y i We have discovered that if one oxyalkylates c0011 glycerol so as to introduce at least three oxyal- 1 kylene radicals for each hydroxyl group, and if H the product so obtained is reacted with a, polyg 000 22313 32 33: g g 2: g ggg then the acyclic reaction product of one mole of tional es ter due to th fe presence of a? le st one oxyeth-yla'ted glycergl g-5 3 2: n 1 a e free carboxyl radical, one can then esterify said ggigfifi may e 1 c y acidic material or intermediate product with at leastone mole of an alcoholic compound of the (CI l )n' )n" type herein described to give a variety of new 0 O C H 0 compositions of matter which have utility in varr a ious arts, and particularly, in the demulsification 35 in which n" has the value of one or two. Simprc$i$l2 fiia rffifii fiii ar isfi if 2e"t 2% i a in ica e 0 ally manufactured by following one of two genfgfi g f fgfigf m y be y In one of said procedures the oxyalkylated glycerol, which is, in essence, a 40 (CQHAO)n'OOCR( )n" polyhydric alcohol, is reacted with a polybasic camorwzmmwooom'cOOH) acid as to give an acidic material or intermediate product, which, in turn, is reacted with an alcoholic body of g g g ig f' Likewise, if three moles of a polybasic acid are Genericaflrlly g alcogonc g i g 45 employed, fthe colmpound may be indicated by the o in orm a: in contemplated may be considered a member fol] w 8 of the class in which m may vary from 1 to 10, (GBHAO)1\'OOCR(COOH)" although the specific significance of m in the oanioi(cimo ooomcoomw present instance will be hereinafter indicated. 6 (czflowoocmeoomfl, The second procedure is to react an alcohol of the formula type R1(0H)m with a polybasic acid so as If a fractional ester of the kind exemplified by to produce an intermediate product, and then the three preceding formulae is reacted with one react said intermediate product or fractional or more moles of an alcohol of the kind prevwusly described in a generic sense as R1(OH) m, then ob- 'viously,'one may obtain a material of the type indicated by the following formula:

cmon'ooomooonnd.

clams-ammon a],

(om.o).'0ocn coonow inwhichzisii, 1 or 2.1lis0, lor2,andzis1,.2or

3,anda:'is0or1,anduislor2.

It has been previously stated that compounds of the type herein contemplated may be obtained by oxyalkylating agents, without being limited to ethylene oxide. Suitable oxyalkylating agents include ethylene oxide, propylene oxide, butylene oxide and glycid, which, although not included,

strictly speaking, by the unitary structure.

, monomer.

reality, obtain a polymer in the sense, for example, thatpolyethylene glycols represent a polymer of ethylene glycol. The term polymer is frequently used to indicate the polymerized product derived from a monomer in which the polymer has the same identical composition as the In the present instance, however, polymerization involves the splitting and loss of water so that the process is essentially selfesterificatlon. Thus, strictly speaking the polymeric compounds are not absolutely isomers of the monomeric compounds, but since, for all practical purposes, they can be so indicated, and since such practice is common in the arts concerned with materials of this type, it is so adopted here. Thus, reference in the appended claims to polymers is intended to include the self-esterlfication products of the monomeric compounds.

stituted ammonium radical, or by. an organic group derived from an alcohol, such as an allphatic alcohol, an aralkyl alcohol, or an alicyclic alcohol. It may also be converted into an amide, including a polyamino amide. Thus, the preceding formula may be rewritten in its broader scope, as follows:

in which n replaces the numbers 2, 3 or 4, Z includes the acidic hydrogen atom itself. In the above formula and hereafter, for convenience, R1 is intended to include any hydroxyl group that remains.

If the compounds herein contemplated are obtained under usual conditions, at the lowest temperatures, then the monomeric form is most likely to result.

The production of the compounds herein contemplated is the result of one or more esteriflcation steps. As is well known, estrification procedures can be carried out in various manners, but generally speaking, esterifications can be carried out at the lowest feasible temperatures by using one or several procedures. One procedure is to pass an inert dried gas through the mass to be esteriiied, and have present at the same time a small amount of a catalyst, such as dried HCl gas,

a dried sulfonic acid, or the like. Another and better procedure, in many instances, is to employ the vapors of a suitable liquid, so as to remove any water formed and condense both the vapors of the liquid employed and the water in such a manner as to trap out the water and return the liquid to the reacting vessel. This procedure is commonly employed in the arts, and for convenience, reference is made to U. S. Patent No. 2,264,759, dated Decemberz, 1941, to Paul C. Jones.

Referring again to the last two formulae indicating the compounds under consideration, it can be readily understood that such compounds, in

numerous instances, have the property of poly-' functionality. In view of this fact. where there is at least one residual carboxyl and at least one residual hydroxyl, one would expect that under suitable conditions, instead of obtaining the monomeric compounds indicated, one would, in

exam, or the like.

In view of what has been said, and in view of the recognized hydrophile properties of the recurring oxyalkylene linkages, particularly the oxyethylene linkage, it is apparent that the materials herein contemplated may vary from compounds which are clearly water-soluble through selfemulsifying oils, to materials which are balsamlike and sub-resinous or semi-resinous in nature. The compounds may vary from monomers to polymers, in which the unitary-structure appears a number of times, for instance, 10 or 12 times. It is to be noted that true resins, i. e., truly insoluble materials of a hard plastic nature, are not herein included. In other words, the polymerized compounds are soluble to a fairly definite extent,

for instance, at least 5% in some solvents, such as water, alcohol, benzene, dlchloroethyl ether, acetone, cresylic acid, acetic acid, ethyl acetate, di-

Thi is simply another way of stating that the polymerized product contemplated must be of the sub-resinous type, which is commonly referred to'as an A resin, or a B resin, as distinguished from a C resin, which is a highly infusible, insoluble resin (see Ellis, Chemistry of Synthetic Resins (1935), pages 862, et seq.).

Reviewing the form as presented, it is obvious that one may obtain compounds within the scope disclosed, which contain neither a free hydroxyl nor a free carboxyl group, and one may also obtain a. compound of the type in which there is present at least one free carboxyl, or at least, one free hydroxyl, or both. The word polar has sometimes been used in the arts in this particular sense to indicate the presence of at least one free hydroxyl group, or at least, one free carboxyl group, or both. In the case of the free carboxyl group, the carboxylic hydrogen atom may, of course, be replaced by any ionizable hydrogen atom equivalent, such, for example, as a metal, an ammonium radical, a substituted ammonium radical, etc. In the hereto appended claims the word "polar is used in this specific sense.

We are aware that compounds similar to those contemplated in the present instance may be derived from polyhydroxylated compounds having more than three hydroxyl groups. For instance, they may be derived from acycylic diglycerol, triglycerol, tetraglycerol, mixed polyglycerols, mannitol, sorbitol, various hexitols, duloltol, pentaerythritol, sorbitan, mannitan, dipentaerythritol monoether and other similar compounds. Such partlcular types in which higher hydroxylated materials are subjected to oxyalkylation and then employed in the same manner as oxyalkylated glycerol, is employed in the pres when present in a low molal type of compound prior tooxyalkylation, reference beingmade to polyhydroxylated materials, including those having two or three hydroxyl groups, as well as those having more than three hydroxyl groups. For instance, the oxyalkylated derivatives, particularly the oxyethylated derivatives of ethyldiethanolamine, bis(hydroxyethyl) acetamide, the acetamide of tris(hydroxymethyl) aminomethane, tetrahydroxylated ethylene diarnine, etc. Compounds may also be derived from cyclic diglycerol and the like.

Furthermore, for convenience, attention is directed to a somewhatsimilar class of materials which are described in our application Serial No.

401,377, filed July 7, 1941, which subsequently matured as U. S. Patent No. 2,324,489, dated July 20, 1943. Said application involves the use of the same type of alcoholic bodies for reactants, but is limited, among other things, to the compounds which are essentially symmetrical in nature, for. instance, involving the introduction of two alcoholic residues, whereas, in the present instance, one, two, or three, or more, might be introduced.

As indicated previously, the polybasic acids employed are limited to the type having not more than 8 carbon atoms, for example, oxalic, malonic, succinic, glut'aric, adipic, maleic; and phthalic. Similarly, one may employ acids such as fumaric, glutaconic, and various others, such as citric, malic, tartaric, and the like. The selection of the particular tribasic or dibasic acid employed, is usually concerned largely with the convenience of manufacture of the finished ester, and also the price of the reactants. Generally speaking, phthalic acid or anhydride tends to produce resinderivatives obtained by oxyethylation, although,

as previously pointed out, other oxyalkylating agentsmay be employed.

As-far as the range of oxyethylated glycerols employed as reactants is concerned, it is our preference to employ those in which approximately to 24 oxyethylen groups have been introduced into a, singleglycerol molecule. This 2,324,489, dated July 20, 1943. The reactants thus contemplated include the type in which there is an amino or amido nitrogen atom, particularly,

means that approximately fiveto eight oxyethylene radicals hav been introduced for each original hydroxyl gr up.

The oxyalkylation of glycerol is a well-known procedure (see Example 11 of German-Patent No.

- German patent.

ous materials, and greater care must be employed if the ultimate or final product be of a sub-resinous type. Specifically, the preferred type of polybasic acid is such as to contain six carbon atoms or less. Generally speaking, the higher the temperature employed, the easier it is to obtain large yields of esterifled product, although polymerization may be stimulated. Oxalic acid may be comparatively cheap, but it decomposes readily at slightly above the boiling point of water. For

. this reason it is more desirable to use an acid which is more resistant to pyrolysis. Similarly, when a polybasic acid is available in the form of an anhydride, such anhydride is apt to produce the ester with greater ease than the acid itself. For'this reason, maleic anhydride is particularly adaptable, and also, everything else employed. Furthermore, reference is made to 605,973, dated November 22, 1934, to I. G. Farbenindustrie A. G.). The procedure indicated in the following three examples is substantially identical with that outlined in said afore-mentioned OxYs'rrrYLAran GLYCEROL.

Example 1 184 pounds of glycerol are mixed with /2%, by weight, of caustic soda solution having a specific gravity of 1.383. The caustic soda acts as a catalyst. The ethylene oxide is added in relatively small amounts, for instance, about 44 pounds at a time. The temperature employed is from C. Generally speaking, the gauge pressure during the operation approximates 200 pounds at the maximum, and when reaction is complete, drops to zero, due to complete absorption of the ethylene oxide. When all of the ethylene oxide has been absorbed and the reactants cooled, a second small portion, for, instance, 44 more pounds of ethylene oxide, are added and the procedure repeated until the desired ratio of 15 pound moles of ethylene oxide to one pound mole of glycerol is obtained. This represents 660 pounds of ethylene oxide for 92 pounds of glycerol.

OxYE'rHYLA'rED GLYCEROL Example 2 The ratio of ethylene oxide is increased to 21 pound moles for each pound mole of glycerol. Otherwise, the same procedure is followed as in Example 1, preceding.

OXYETHYLATED GLxcaRoL Example 3 The same procedure isfollowed as in the two previous examples, except that the ratio of ethylene oxide to glycerol is increased to 21 to 1.

OxYa'mYLArrm GLYCEROL Mum-r2:

Example 1 OX-YETHYLATED GLYCEROL MALEATE Example 2 The same procedure is followed as in the preceding example, except that two moles of maleic anhydride are employed so as to obtain the dimaleate instead of the monomaleate.

OXYETHYLATED GLYCEROL MALnAfl:

I Example 3 The same procedure is followed as in the two preceding examples, except that three moles of maleic anhydride are employed so as to obtain the trimaleate.

Oxrsrnnsrn GLYCIROL Mann-rs Example 4 The same procedure is employed as in the pre--' ceding examples, except that onycthylated glycerol (ratio 1 to 18) is substituted in place of oxyethylated glycerol (ratio 1 to 15).

OxYarr-rYLA'rsn GLYenaor. Mann's:

' Eatample 5 The same procedure is employed as in the preceding examples, except that oxyethylated glycerol (ratio 1 to 21) is employed instead of oxyethylated glycerol (ratio 1 to 15) or (1 to 18).

Previous reference has been made to an alcoholic body which has been defined generically by the formula R1(OH)m. The sub-generic class of alcoholic compounds employed as reactants in the manufacture of the present compounds, are

hydroxylated acylated monoamino bodies free from ether linkages and of the following formula:

m+m'+m"=3. One can obtain or manufacture chemical compounds whose composition is indicated by the following formulae:

If, in the above formulae, T represents an amino hydrogen atom, as well as a substituent therefor, then the formulae above described may be summarized by the following formula:

R.C OO-CSHI) as (0H.C:Hi)n' However, the radical C1 54. which appears in the above formula, may represent any similar radical, such as a CsHe radical, a Cilia radical,

etc., and therefore, the above formula may be indicated as follows:

(OHeCI I) n in which R000 represents the oxyacyl radical derived from a monobasic detergent-forming acid; T represents a hydrogen atom or a nonhydroxy hydrocarbon radical, or the acylated radical obtained by replacing a hydrogen atom of-the hydroxyl group of an alkylol radical by the acyl radical of a monobasic cal-boxy acid having less than 8 carbon atoms: 1: represents a small whole number, which is less than 10; m represents the numeral 1, 2, or 3; 111. represents the numeral 0, 1 or 2: and m" represents the numeral 0, 1 or 2, with the proviso that In the above formulae it has been pointed out that T represents a hydrogen atom, or a nonhydroxy aliphatic hydrocarbon radical, such as a methyl radical, ethyl radical, propyl radical, amyl radical, octadecyl radical, etc. However, T may also represent a non-hydroxy alicyclic radical, such as a cyclohexyl radical, or a nonhydroxy' aralkyl radical, such as a benzyl radical; or T may represent the acylated radical obtained by replacing a hydrogen atom of the hydroxyl group of an alkylol radical, or the equivalent thereof, by the acyl radical of a monobasic carboxy acid, such as acetic acid, butyric acid, heptoic acid, or .the like, all of which are characteriaed by having less than 8 carbon atoms. The alkylol radical priorto a'cylation, may be a hydroxy alicyclic or a hydroxy aralkyl radical, provided the hydroxy radical is attached to the aliphatic residue of the aralkyl radical.

In the above formula, as has been pointed out, R 000 represents the oxyacyl or acid radical derived from the acid ECOOH. R.COOH represents any monobasic detergent-fuming carbon acid, such as a typical fatty acid or abietic acid or naphthenic acid. a

Typical fatty acids are those which occur in naturally-occurring oils and fats, and generally have 8 or more carbon atoms and not over 32 carbon atoms. Common examples include olelc acid, stearic acid, linoleic acid, linolenic acid, ricinoleic acid, erucic acid, palmi-tic acid, myristic acid, etc. These acids combine with alkali to produce soap or soap-like materials, and are commonly referred to as being monobasic detergent-forming carboxy acids.

The alkylol radical, previously referred to, prior to esterification, may be a hydroxy alicyclic or a hydroxy aralkyl radical, provided the hy droxy radical is attached to the aliphatic residue of the aralkyl radical.

As to the amines above described, which happen to betertiary amines, it may be well to point out that these may be formed readily by a reactioninvolving an ester of the selected detergentforming acid, for instance, a fatty acid ester,

such as the glyceride, and a corresponding amine. I This may be illustrated in the following manner:

If triethanolamine, employed in the above formula, is replaced by ethyl diethanolamine, then one would obtain one of the remaining types of tertiary amines illustrated. Reference is made to Patent No. 2,167,349, dated July 25, 1939, to De Groote, Keiser and Blair.

In the remaining type of material there is an amino hydrogen atom present. The manufacture of such material may be illustrated by the following reactions:

However, if maximum yields are not necessary, one need not resort to reactions of the kind previously described to produce secondary amines, but one may employ the following type of reaction:

OH.CsHtNHa Suitable primary and secondary amines, which may be employed to produce materials of the kind 7 above described, include the following: Diethanolamine, monoethanolamine, ethyl ethanolamine, methyl ethanolamine, propanolamine, dipropanolamine, propyl propanolamine, etc. Other examples include cyclohexylolamine, 'dicyclohexylolamine, cyclohexyl ethanolamine, cyclohexyl propanolamine, benzylethanolamine, benzylpropanolamine, pentanolamine, hexanolamine, octylethanolamine, octadecylethanolamine, cyclohexanolethanolamine, etc.

Similarly, suitable tertiary amines which may be employed include the following: Triethanolamine, diethanolalkylamines, such as diethanol ethylamine, diethanol propylamine; etc. Other examples include diethanol methyiamine, trlpropanolamine, dipropanolmethylamine, cyclohexanol, diethanolamine, dicyclohexanol ethanolamine, cyciohexyl diethanolamine, dicyclohexyl o ethanolamine, dicyclohexanol ethylamine, ben- Reference is again made to the formula which summarizes the various hydroxylated amines used as intermediate raw materials, via:

(R.C O O.CnHin) n (OH-Can) I? in which the characteristics have their previous significance. Attention is directed to the fact that where the substituted alkyl radical on.a.ooo.on

appears, a suitable non-aryl radical other than an aliphatic residue may serve as the functional equivalent; for instance, an alicyclic radical deinclude the alicyclic radical or residues, or the aralkyl radicals or residues which are the equivalent thereof. There is no intention to include an aromatic radical where there is a direct linkage between the aromatic nucleus and the amino hydrogen atom, for the reason that such products have little or no basicity and do not have the characteristic properties of the amines previously described.

In indicating the various hydroxylated tertiary amines of the non-aryl type, which may be employed to produce the amine contemplated as the demulsifying agent of the present process, it is desirable to mention that amines of the type where Ia hydroxyl acyl radical replaces a hydrogen orhoinr 11.000 ormim .R.C00-C:Hs 03.01114 R.COO H 3 R-COO-CsHA 011.0311: H+O:Ht(0H)a 3.000 orncim ucoo-cim ouoiHiNHi B.coo oncirnms, a Rcoo.ciHiNm+cim(on atom of the hydroxyl radical of the hydroxy tertiary amine, are not included within the broad class of hydroxy tertiary amines, unless there is another hydroxyl radical attached to the usual' alkyl radical. For instance, ifethyl diethanolamine is treated with two moles of lactic acid so as to form the dilactyl compound of the following formula:

cmoHc-o-onn omens-o-mm-rr then it is understood that such materials would not represent a hydroxy tertiary amine within the meaning or scope, as herein employed. If, on the other hand, triethanolamine were treated with lactic acid, so as to give monolactyl triethanolamine of the following composition:

then such compound would be included, due to the presence of one or more hydroxyl radicals at- 'ached to the allgyl radicals.

Similarly, in indicating the various hydroxylated primary or secondary amines of the nonaryl type, which may be employed to produce the amine contemplated as the demulsiiying agent of the present process, it is desirable to indicate that amines of the type where a hydroxy acyl radical replaces a hydrogen atom of the hydroxyl radical of a hydroxy primary or secondary amine, are not included within the broad class of hydroxy tertiary amines, unless there is another hydroxyl radical attached to the usual alkyl radical. For instance, if ethanolamine is treated with lactic acid soas to form the lactyl derivative of the following formula:

then it is understood that such materials would not represent a hydroxy primary amine within the meaning or scope, as herein employed. The same would be true if the corresponding product were derived from diethanolamine, provided both hydroxy radicals had been esterified, with lactic acid.

The manufacture of compounds from tertiary amines is relatively simple, because no precautions are necessary to prevent amidification. .The selected detergent-forming acid, or ester, as, for example, a fatty oil and the selected hydroxy tertiary amine, are mixed in suitable proportions and heated at some point above the boiling point of water, for instance, 110 C., and at a point helow the decomposition point of the amine or the fatty oil, for instance, 180 C., for a suitable period of time, such as two to eight hours. Mild agitation is employed. A catalyst, such as sodium oleate, sodium carbonate, caustic soda, etc., may be present in amounts of about one-half of 1%, or less. It is noted that the fatty acids are employed in this instance, in the form of an ester,

to wit, the glyceride, although, as previously.

pointed out, other functional equivalents can be readily employed with equal facility. It is to be noted that the reactions above described do not take place to any appreciable extent if the fatty acid has been converted into the soap or salt.

Such salts are not functional equivalents. As previously indicated, an ester of abietic acid or naphthenic acid might be employed, if desired.

When, however, one i employing a,hydroxy secondary amine, precautions must be taken, so that one gets a substantial percentage of products derived by esteriflcation, rather than amidiflcation. Any suitable ester may be employed, but it is often most convement to employ the glyceride of a fatty acid, for instance, triricinoleln. The selected glyceride and the selected hydroxy secondary amine are mixed in suitable proportions and heated at some point above the boiling point of water, for instance, 110 0., and below the decomposition point of the amine or fatty material, for instance, 180 0., for a suitable period of time, such as 4-24 hours. Mild agitation is employed. A catalyst, such as sodium oleate, sodium carbonate, caustic soda, etc., may be present in amounts of about or less. It is to be noted that the fatty acids are present in ester form and not in the form of the free acid, and thus there is no tendency to form the salt to any marked exis an amino hydrogen atom attached to the amino nitrogen atom can be treated with an oxyalkylating agent such as ethylene oxide, propylene oxide, glycidcl, or the like, so as to introduce a hydroxy hydrocarbon radical. In the event that no hydroxy hydrocarbon radical is available for reaction with a material such as'nonaethylene glycol dlhydrogen dimaleate, then in that event the acyl radical present must contain a hydroxyl radical. In other words, one must employ ricinoleic acid, hydroxystearic acid, or some similar equivalent.

COMPLETED MONOMERIC DE uvA'rIvE Example 1 One pound mole of a product of the kind described under the heading Oxyethylated glycerol maleate, Example 1, is reacted with one pound mole of an ester obtained by reacting triethanolamine with ricinoleic acid. Such reaction may be conducted in the presence of an inert vaporizing solvent. However, if an inert vaporizing solvent is employed, it is generally necessary 'to use one which has a higher boiling range than xylene, and sometimes removal of such solvent might present a difliculty. In other instances, however, such high boiling inert vaporizing solvent, if employed,might be permitted to remain in the reacted mass and, appear as a constituent or ingredient of the final product. In any event, our preference is to conduct the reaction in the absence of any such solvent and permit the reaction to proceed with the elimination of water. The temperature of reaction is about to 200 C. and time of reaction about 20 hours.

COMPLETED, MONOMERIC DERIVATIVE Example .2

COMPLETED MONOMERIC DERIVATIVE Example 3 The same procedure is followed as in the two preceding examples, except that the trimaleate is substituted for the monomaleate or dimaleate in the two preceding examples.

COMPLETED MONOMERIC DERIVATIVE Example 4 The same procedure is followed as in Examples 2 and 3, immediately preceding, except that for each pound mole of the maleate, or each pound mole of the trimaleate, instead of using one pound mole of monoricinoleic acid ester of triethanolamine, one employs two pound moles.

COMPLETED MONOMERIC DERIVATIVE Example 5 I I The same procedure is followed as in Example 3, preceding, except that for each pound mole of trimaleate, instead of adding one pound mole of monoricinoleic acid ester of triethanolamine, one adds three pound moles of monoricinoleic acid ester of triethanolamine for reaction.

COMPLETED MONOMERIC DERIVATIVE Example 6 Reference to the preceding examples will show that in each and every instance oxyethylated glycerol (ratio 1 to has been employed as a raw material or primary reactant. In the present instance, a. more highly oxyethylated glycerol is employed, to wit, one involving the ratio of 1 to 18. (See Oxyethylated glycerol maleate, Example 4, preceding.)

COMPLETED MONOMERIC DERIVATIVE Example 7 The same procedure is followed as in Example 6, immediately preceding, except that the oxyethylated glycerol employed represents one having an even higher degree of oxyethylation. For

example, one indicated by the ratio of 1 to 21.

- (See Oxyethylated glycerol maleate, Example 5,

preceding.)

COMPLETED MONOMERIC DERIVATIVE Example 8 The ricinoleic acid ester of ethyldiethanolamine is substituted for the ricinoleic acid ester of triethanolamine in the preceding examples.

COMPLETED MONOMERIC DERIVATIVE Example 9 stantly during the heating and esterification step. If desired, an inert gas, such as dried nitrogen or'dried carbon doxide, may be passed through the mixture. Sometimes it is desirable to add an esterification catalyst, such as sulfuric acid, benzenesulfonic acid, or the like. This is the same general procedure as employed in the manufacture of ethylene glycol dihydrogen diphthalate. March 30, 1937, to Frasier.)

(See U. S. Patent No. 2,075,107, dated Sometimes esterification is conducted most readily in the presence'of an inert solvent, that such type of reaction involves an acid anhydride,

such as maleic anhydride, and a glycol. However, if water is formed, for instance, when citric acid is employed, then a solvent such as xylene may be present and employed to carry off the water formed. The mixture of xylene vapors and water Vapors can be condensed so that the water is separated. The xylene is then returned to the reaction Vessel for further circulation. This is a conventional and well known procedure and requires no further elaboration.

In the previous monomeric example there is a definite tendency, in spite of precautions, at least in a number of instances, to obtain polymeric materials and certain cogeneric by-products. This is typical, of course, of organic reactions of this kind, and as is well known, organic reactions per se are characterized by the fact that yields are the exception, rather than the rule, and that significant yields are satisfactory, especially in those instance where the by-products or congeners may satisfactorily serve with the same purpose as the principal or intentional product. This is true in the present instance. In many cases when the compound is manufactured for purposes of demulsification, one is better off to obtain a polymer in the sense previously described, particularly a polymer whosemolecular weight is a rather small multiple of the molecular weight of .the monomer. For instance, a polymer whose molecular weight is two, three, four, five, or six times the molecular weight of the monomer. Polymerization is hastened by the presence of an alkali, and thus in instances where it is necessary to have a maximum yield of the monomer, it may be necessary to take such precautions that the alkali used in promoting oxytheylation of glycerol, be removed before subsequent reaction. This, of course, can be done in any simple manner by conversion to sodium chloride, sodium sulfate, or any suitable procedure. 1

In the preceding examples of the completed monomeric derivatives, Examples 1 to 10, inclusive, no reference is made to the elimination of such alkaline catalyst, in View of theefiectiveness' of the low multiple polymers as demulsifiers. Previous reference has been made to the fact that the carboxylic hydrogen atom might be variously replaced by substituents, including organic radicals, for instance, the radicals obtained from alcohols, hydroxylated amines, non-hydroxylated amines, polyhydric alcohols, 'etc. reverse is also true, in that a free hydroxyl group may be esterified with a selected acid, varying from such materials as ricinoleic acid to oleic acid, including alcohol acids, such as hydroxyacetic acid, lactic acid, ricinoleic acid and also polybasic acids of the kind herein contemplated.

With the above facts in mind, it becomes obvious that what has been previously said as to polymerization, with the suggestion that byone can readily appreciate that the formation of heat-rearranged derivatives or compounds must take place to a greater or lesser degree. Thus, the

products herein contemplated may be characterized by being monomers of the type previously described, or esteriflcation polymers, or the heat- Obviously, they rearranged derivatives of the same, and thus including the heat-rearranged derivatives of both the polymers and esterification monomers, separately and Jointly. Although the class of materials specifically contemplated in this instance is' a comparatively small and narrow class of a broad genus, yet it is obviously impossible to present any adequate formula which would contemplate the present series in their complete ramification, except in a manner employed in th hereto appended claims.

Although the products herein contemplated vary so broadly in their characteristics, 1. e., monomers through sub-resinous polymers, soluble products, water-emulsiflable oils or compounds, hydrotropic materials, balsams, subresinous materials, semi-resinous materials, and the like, yet there is always present the characteristic unitary hydrophile structure related back to oxyalkylation, particularly the oxyethylation of the glycerol used as the raw material. When our new compound is used as a. demulsifier, in the resolution of oil field emulsions, the demulsiiler may be added to the emulsion at the ratio of 1 part in 10,000, 1 part in 20,000, 1 part in 30,000, or for that matter, 1 part in 40,000. In such ratios it well may be that one cannot differentiate between the solubility of a compound completely soluble in water in any ratio, and a semi-resinous product apparently insoluble in water in ratios by which ordinary insoluble materials are characterized. However, at such ratios the importance must reside in interfacial position and the ability to usurp, preempt, or replace the interfacial position previously occupied perhaps by the emulsifying colloid. In any event, reviewed in this light, the obvious common property running through the entire series, notwithstanding variation in molecular size and physical make-up, is absolutely apparent. Such statement is an obvious over-simplification of the rationale underlying demulsification, and does not even consider the resistance of an interracial film to crumbling, displacement, being forced into solution, altered wettability, and the like. As to midiflcation polymers, for instance, where Z is a .polyamino amide radical, see what is said subsequently.

Comrnsrnn POLYMERIC Dmuvarrvns Incmomc Hear-Resumes!) Cosamzas Example 1 A polyiunctional monomer of the kind described previously, for instance, the one obtained by reacting polyethylated glycerol dimaleate with the monori cinoleic acid ester of triethanolamine is heated at a temperature of approximately 220-240" C., with constant stirring, for a period of 2-60 hours, so as to eliminate sufllcient water in Order to insure that the resultant product has a. molecular weight approximately twice that of the.

Courtnrln POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED Coo-mums Example 2 Courunn Potmiuc DERIVATIVES Incmnmc Hmr-Rmaamomn Coammas Example 3 The same-procedure is followed as in Examples 1 and 2, preceding, except that one employs reactants derived from tripropanolamine instead of triethanolamine.

Courtlrnn Pormsarc Daarvxrrvns Incmnmc Han-Resumes Coaanaas Emample 4 The same procedure is followed as in Examples 1 to 3, preceding, except that one polymerizes a mixture instead of a single monomer, for instance, a mixture of materials of the kind described in Completed monomeric derivative, Example 3, and in Completed monomeric derivative, Example 4,

' are mixed in molecular proportion and subjected to polymerization in the manner indicated in the previous examples.

It is understood, of course, that the polymerized product need not be obtained as a result of a twostep procedure. In other words, one need not convert the reactants into the monomer and then subsequently convert the monomer into the polymer. The reactants may be converted through the monomer to the polymer in one step. Indeed, the formation of the monomer and polymerization may take place simultaneously. This is especially true if polymerization is conducted in the absence of a liquid such as xylene, as previously described, and if one uses a comparatively higher temperature, for instance, approximately 200 C. for polymerization. Thus, one pound mole of an oxyethylated glycerol polymaleate of the kind previously described is mixed with one pound mole of the monoricinoleic acid ester of triethanolamine, and such mixture reacted for 20 hours at approximately 200 until the reaction mass is homogeneous. It is stirred constantly during reaction. Polyfunctionality may reside in dehydration (etherlzation) of two hydroxyl groups attached to dissimilar molecules.

The fact that the, polymerized and heat-arranged products can be made in a single step, il-

lustrates a phenomenon which sometimes occurs either in such instances where alcoholic bodies of the kind herein illustrated are contemplated as reactants, or where somewhat kindred alcoholic bodies are employed. The reactants may be mixed mechanically to give a homogeneous mixture, or if the reactants do not mix to give a homogeneous mixture, then early in the reaction stage there is formed, to a greater or lesser degree, sufficient monomeric materials so that a homogeneous system is present. Subsequently, as reaction continues, jthe system may become heterogeneous and exist in two distinct phase, one being possibly an oily; body of moderate viscosity, and the other being a heavier material, which is sticky or subresinous in nature. In many instances it will be found'that the thinner liquid material is a monomer and the more viscous 0r resinous material is a polymer, as previously described. Such product can be used for demulsiflcation by adding a solvent which will mutually dissolve the two materials, or else, by separating the two heterogeneous phases and employing each as if it were a separate product of reaction.

Materials of the kind herein contemplated may find uses as wettin8, detergent, and leveling agents in the laundry, textile, and dyeing industry; as wetting agents and detergents in the acid washing of fruit, in the acid washing of building stone and brick; as a wetting agent and spreader in the application of asphalt in road building and the like, as a constituent of soldering flux preparations; as a flotation reagent in the flotation separation of various minerals; for flocculation and coagulation of various aqueous suspensions containing negatively charged par-.- ticles such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifiers for cosmetics, spray oils, water-repellent textile finish, etc. These uses are by no means exhaustive.

However, the.most important phase of the present invention, as far as industrial applica--v tion goes, is concerned with the use of the materials previously described as a demulsifier for water-in-oil emulsions, and more specifically, emulsions of water or brine in crude petroleum. -We have found that the particular chemical compounds or reagents herein described may also be used for other purposes, for instance, as a break inducer in doctor treatment of the kind intended to sweeten gasoline. (See U. S. Patent No. 2,157,223, dated May 9, 1939, to Sutton).

'cals having not over 18 carbon atoms; 11. represents a small whole number which is less than 10;

I 112 represents a numeral-varying from 1 to 3; m

represents a numeral varying from to 2; and m" represents a numeral varying from 0 to 2, with the proviso that m+m'+m"=3; the acyl radical substituted for a reactive oxygen-linked hydrogen atom of said acylated basic aminoal- Chemical compounds of the kind herein described are also of value as surface tension depressants in the acidization of calcareous oilbearin'g strata by means of strong mineral acid, such as hydrochloric acid. Similarly, some members are effective as surface tension depressants or wetting agents in the flooding of oil-bearing strata.

As to using compounds of the kind hereindescribed as flooding agents for recovering oil from subterranean strata, reference is made to the procedure described in detail in U. S. Patent No. 2,226,119, dated December 24, 1940, to De Groote and Keiser. As to using compounds of the kind herein described as demulsiflers, or in particular 'as surface tension depressants in combination with mineral acid or acidization of oil-bearing strata, reference is ,made to U. S. Patent No. 2,233.383, dated February 25, 1941, to DeGroote and Keiser.

Cognizance must be taken of the fact that the surface of the reacting vessel may increase or decrease reaction rate and degree of polymerization, for instance, an iron reaction vessel speeds up reaction and polymerization, compared with a glass-lined vessel.

As has been previously indicated the subgenus employed as an alcohol in the present instance is one of a series of alcoholic compounds which are contemplated in our co-pending applications Serial Nos. 497,118, 497,119, 497,120, 497,121, 497,122, 497,123, 497,124, 497,125, 497,126,

497,134, and 497,135, all filed August 2, 1943.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. A member of the class consisting of subresinous ester-linked acylated derivatives of a basic aminoalcohol of the following formula:

(RzCOO.CnH-1n) m Nun."

oaonimm' atoms; T represents a member of the class consisting of hydrogen atoms and hydrocarbon radiexhausted cohol being the acyl group of an acidic fractional ester ofthe formula:

I [(RO),,'OOCR|COOH]..'- in which --OCR1CO is the acyl radical of a polycarboxy acid having not over 8 carbon atoms; Z represents a metallic cation; R-O is a member of the class consisting of ethylene oxide radicals, propylene oxide radicals, butylene oxide radicals and glycid radicals, and n represents a numeral varying from 3 to 10, and n" represents a numeral varying from 0 to '2, and n' represents a numeral varying from 1 to 3, with the proviso that the sum of n" '+n=3.

, 2. The ester of claim 1, wherein m." is 0.

3. Theester of claim 1, wherein m" is 0 and m is 1. 1 .4. The ester of claim 1, wherein m" is .0; m is 1 and RzCOO is the acyloxy radical of a higher fatty acid having 18 carbon atoms.

5. The ester of claim 1, wherein the m" is 0; m is one; RsCOO is the acyloxy radical of a higher fatty acid having 18 carbon atoms and at least one ethylene linkage.

6. The ester of claim 1, wherein the m" is 0; m is one; RzCOO is the acyloxy radical of a higher fatty acid having 18 carbon atoms and at least oneethylene linkage, and n is 2.

7. The ester of claim 1, wherein the m" is 0; m is one; RzCOO is the acyloxy radical of a higher fatty acid having 18 carbon atoms and at least one acid is dioarboxy.

9. The ester of claim 1, wherein the m" is 0; m is one; R2COC is the acyloxy radical of a higher fatty acid having 18 carbon atoms and at least one ethylene linkage; n is 2, R-O is an ethylene oxide radical, and OCR1CO is a maleic acid radical.

10. The ester of claim 1, wherein the m" is 0; m

is one; R1000 is the acyloxy radical of a higher fatty acid having 18 carbon atoms and at least one ethylene linkage; n is 2; 18-0 is an ethylene oxide radical, and --OCRiCO- is a phthalic acid radica 11..-The ester of claim 1, wherein the m" is O; m is one, R2000 is the acyloxy radical of a higher fatty acid having 18 carbon atoms; at least one ethylene linkage; n is 2; R,-O is an ethylene oxide radical, and -OCR1CO is an adipic acid radi-,

cal.

12. The method of manufacturing esters described in claim 1, which consists of reacting an acylated aminoalcohol of the following formula:

moooonimm -Cn 2n m in which RzCOO represent the acyloxy radical ofa monocarboxy detergent-forming acid having in which 0CR.1CO- is the acyl radical of a polycarboxy acid having not over 8 carbon atoms; Z represents a metallic cation; R-O is a. member of the class consisting of ethylene oxide radicals, propylene oxide radicals, butylene oxide radicals and glycid radicals, and n represents a numeral varying from 3 to 10, and n" represents a numeral varying from 0 to 2, and n'" represents a numeral varying from 1 to 3, with the proviso that the sum of nII+nIII 3I MELVIN DE GROOI'E. BERNHARD KEISER. 

